DE4422865A1 - Process for the production of aminated fibers from regenerated cellulose - Google Patents

Description

The present invention is in the field of textile dyeing Viscose fibers.

Viscose fibers have the same dyeing properties, including regenerated cellulose fibers called, essentially that of cotton fibers. At the current status of Technology is for dyeing cellulosic natural or regenerated fibers Alkaline agents as well as electrolytes are necessary in order to be satisfactory To achieve fixing results with reactive dyes. Just these necessary However, additives represent unacceptable environmental pollution. For the Regenerate fibers are therefore becoming increasingly important in the future on cellulose, which can be dyed without salt or alkali. There is a possibility in modifying the viscose fibers so that their chemical Behavior similar to animal fibers, such as wool or silk, and among neutral ones Conditions with anionic dyes without additional salt or alkali can be colored.

Modifications of viscose have already been described in the literature. The DE-A-19 48 487, for example, describes a process for the production of Viscose fibers with changed dyeing properties. The production turns out but extremely complex and uneconomical. Beyond that Polyaminamides are used that preserve the native character of the fiber predominantly interfere with the lipophilic structure of the additives used. This is the case, for example, with the use of disperse dyes expressing later coloring.  

Also, the addition of amine compounds to improve the physical Properties of viscose fibers known. In addition to a variety of mono- or Oligomeric amines are also polymeric compounds such as polyethoxylated Amines or polyalkylene polyamines are described. A summary of Components and their effects is in Götze, chemical fibers after the Viscose process, Springer Verlag 1967, p. 635 ff.

DE-A-14 69 062 also describes aminalized fibers. With the additives are aminoethyl and diethylaminoethyl celluloses in high Concentration, the coloring is done exclusively with acid dyes.

Various are disclosed in EP-A-0 284 010, EP-A-0 359 188 and EP-A-0 546 476 compounds containing amino groups as agents for pretreating the surface of textiles containing cellulose fibers described before the dyeing process. The disadvantage of such processes is an additional process step and yellowing of the fabric.

The object of the present invention was modified viscose fibers To provide textiles made of such fibers with salt and alkali free Color reactive dyes and the disadvantages of the prior art Avoid technology.

It has been found that this object is surprisingly achieved by admixing the following modifiers to a viscose spinning solution or Cellulose solution is dissolved.

The fibers of the invention can be used with reactive dyes without additives stain of alkali and salts. Coloring with acid dyes is also easy possible.  

In addition, these fibers exhibit when used after the viscose process be spun, compared to conventional viscose fibers higher Tear resistance and elongation at break in both dry and wet conditions Condition on.

The present invention relates to modified Regenerated cellulose fibers made by combining a cellulose solution Modifier is added and removed from solution, or by using a viscose solution adds a modifier and spins fibers using the viscose spinning process, characterized in that the modifier is a polyethyleneimine of the formula (I) is

wherein
X is hydrogen or a radical of the formula - (CH₂-CH₂-NH) _c -H,
a is a number from 50 to 600 and
c is a number from 0 to 50,
or is a reaction product of a polyethyleneimine of formula (I) with a bifunctional alkylating agent of formula (II)

A-Z-A (II),

wherein
A is a group of the formula -CH₂-Y, in which Y is a substituent which can be split off as an anion, in particular chlorine, bromine, iodine or -OH or a group which can be split off as an anion, in particular the sulfato group or a sulfonyloxy group, in particular phenylsulfonyloxy or p-tolylsulfonyloxy, or the Epoxy group

means and Z is a direct bond or for a divalent  straight-chain or branched radical of the formula (III)

C _n H _2n (III)

where n is a number from 1 to 4,
a divalent radical of the formula (IV)

-C _m H _2m -DC _m H _2m - (IV)

wherein m represents the numbers 1 or 2 and D represents -O-, -S-, -NH-, -CO-, -SO-, -SO₂- or phenylene;
or is a polymeric reaction product of an epihalohydrin with ammonia or with an amine of the formula (V)

wherein
A is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms,
R alkyl with 1 to 5 carbon atoms, hydroxyalkyl with 1 to 5 carbon atoms, a group of the formula

a group of the formula

where n is a number from 0 to 5 and
X represents oxygen or sulfur;
or R and A together

or an aliphatic heterocycle, which can also contain a further heteroatom from the group O, S and N,
and alkylene are each C₁-C₆-, preferably C₂-C₃-alkylene.

The polyethyleneimine of the formula (I) used is a molecule in which -NH₂, (NH and -N) building blocks are present by ethylene groups are linked together. The polyethyleneimine contains a total of about 50 to 600 ethyleneimine units. In common commercial products, primary, secondary and tertiary nitrogen functions in a numerical ratio of about 1: 2: 1. For reaction with the polyethyleneimine of the formula (I), In principle, all known bifunctional alkylating agents can be used.

Such bifunctional ones are preferred for the reaction with polyethyleneimine Alkylating agents in which A are groups of the formula -CH₂-Y which have a Bridge members of the formula (IV) are linked to one another, or those in which one of the radicals A is a group of the formula -CH₂-Y, which is directly attached to a Epoxy group is bound.

Examples of such bifunctional alkylating agents are epichlorohydrin, Glycid, 1,3-dichloropropan-2-ol, β, β'-dichloro-diethyl ether, β, β'-dichloro diethylamine, β, β'-dichloro-diethyl sulfide, β, β'-dichlorodiethylsulfoxide, β, β'-dichloro diethylsulfone, β, β′-disulfatoethyl ether, β, β′-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzene, meta- or para-diepoxypropylbenzene, Diepoxybutane, diepoxy-2-methylbutane and diepoxypropylamine.  

The polyethyleneimine and the bifunctional alkylating agent are combined in one Weight ratio of 100: 0.01 to 100: 2, preferably from 100: 0.1 to 100: 1, implemented together.

The reaction products to be used according to the invention from a Epihalohydrin with NH₃ or an amine of formula (V) are by Reaction of an epihalohydrin, preferably epichlorohydrin, with ammonia or an amine of formula (V) at temperatures of about 60 to 70 ° C in Water or a lower alcohol as a solvent. These amines can optionally also with C₁-C₄-alkyl groups, preferably C₁-C₃- Alkyl groups, be quaternized. The quaternization can be carried out with alkyl halides, preferably alkyl chlorides or dialkyl sulfonates by known methods be made.

As amines which correspond to the formula (V) listed above, are mentioned for example: monomethyl, ethyl, propyl, isoproyl, butyl, -isobutylamine, monooxethyl-, monooxypropylamine, ethylenediamine, Diaminopropanes, diaminobutanes, diaminohexanes, 3,3′-diaminodipropyl ether, Piperazine, monooxethyl- and di-oxethylethylene diamine, diethylene triamine, Dipropylenetriamine and triethylenetetramine. The making of these connections is described in detail in US-A-3,544,363.

So that the modifiers remain embedded in the fibers and not with the subsequent precipitation, stretching and washing processes are washed out higher molecular weights and therefore longer molecular chains are required. To improve the physical fiber properties is to remain The modifiers in the fibers are not required, but an improvement in the Staining properties can only be achieved if the modifiers in the Fibers remain.

The minimum molecular weights of the modifiers according to the invention for a sufficient storage in the fibers is 400, excellent results  are obtained with molecular weights over 1000.

The amount of the stored in the viscose fibers according to the invention Modifier is advantageously 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%, based on the total weight of the invention modified viscose fibers. Decisive for the amount of used The modifier is the content of amino groups.

Are the fibers of the invention by the viscose spinning process prepared, the cellulose is first broken down alkaline (Alkali cellulose), then reacted with carbon disulfide and then this Viscose solution of the modifier added. In an alternative embodiment the modifier is added directly to the alkaline digested cellulose and then reacted with carbon disulfide to form the xanthate. The Reaction with carbon disulfide is conveniently done at Temperatures from 15 to 30 ° C.

Are the fibers of the invention according to other usual, the expert current process for producing cellulosic fibers from solution, such as the cupro process, the lyocell process and the Process on low substituted cellulose ethers, so produced Cellulose dissolved in a suitable organic solvent with which Modifier implemented and spun directly from the solution into fibers. At the It is best to meter in immediately before spinning, the Interference and homogeneous distribution with the help of known mixing systems static or dynamic mixing systems. The dosing can also be used in any preliminary stage in spinning mass production respectively.

The advantage of the modifier according to the invention is that it is simple technical application, since this as a substance directly or as an aqueous Preparation with a content of over 50% can be used.  

On the one hand, this enables high embeddings and on the other hand negative effects on physical fiber properties Dilution effects can be avoided.

The modifiers according to the invention are particularly suitable for use with viscose fibers, because in addition to the dyeing behavior, the physical Improve the properties of the fibers.

After the dosing, the spinning solutions can be made according to the known methods processed for fiber production. Serious changes in the Procedures are not required. In the viscose spinning process, the from Use of modifiers known process changes, such as. Legs increased stretch, to be used with success.

The filterability of the viscose shows no deterioration in comparison with additive free samples, so that no clogging of the in the course of the spinning process Spinneret can be observed. The deformation of the viscose is done according to usual and known methods, such as. B. with spinnerets, one subsequent precipitating bath and, if appropriate, further post-treatment baths.

The modified regenerated cellulose fibers produced according to the invention can after processing to woven and knitted fabrics using various Processes such as pull-out, block and modern printing processes belong to this also ink jet processes, without the use of additional electrolyte salt or Alkali can be colored with reactive dyes.

The fibers according to the invention are dyeing with reactive dyes significantly more affine than conventional viscose fibers, but differ in the otherwise desired properties, such as handle, hardly compared to the conventional viscose fibers.

Both those after the viscose process and those spun from solution Fibers according to the invention are with reactive dyes without additional alkali  and salt and can be dyed with acid dyes. The after the viscose process spun cellulose fibers according to the invention are also distinguished due to improved dry and wet strengths.

The textile modified fiber material used for the subsequent dyeing process can be used in all processing states, such as yarn, flake, Comb and piece goods (fabric) are available.

The modified textile fiber materials are dyed according to the invention analogous to known dyeing methods and printing processes for dyeing or printing of fiber materials with water-soluble textile dyes and under Application of the temperature ranges known for this and usual amounts of dye, but with the exception that for the dye baths, Padding liquors, printing pastes or ink jet formulations an addition of alkaline acting compounds, as they are usually used to fix fiber-reactive Dyes are used, is not necessary and furthermore on usual Additions to electrolyte salts can be dispensed with.

For example, the different extraction processes are used as dyeing processes, like dyeing on the jigger and on the reel runner or dyeing out long or short liquor, dyeing in jet dyeing machines, dyeing after Block cold dwell process or after a block hot steam fixing process in Consideration. Conventional printing techniques come as printing processes including ink jet printing and transfer printing.

The dyes that are used to dye the modified cellulose are generally anionic in nature. The fiber-reactive ones are particularly suitable Textile dyes containing hydroxyl groups, for example cellulose, or Amino and thiol groups, for example wool and silk, from synthetic polymers, such as polyamides, or those according to the invention aminated celluloses, can react and form a covalent bond  capital. As a fiber-reactive component on the textile dyes especially the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl and Fluorotriazinyl group and combinations of these reactive groups called.

As reactive dyes for dyeing or printing according to the invention modified viscose fibers are all water-soluble, preferably anionic Dyes, preferably one or more sulfo and / or carboxy groups own and contain the fiber-reactive groups. Suitable Dyes can be of the class of azo developing dyes Direct dyes, vat dyes and acid dyes, the Copper complex, cobalt complex and chrome complex azo dyes, copper and Nickel phthalocyanine dyes, anthraquinone, copper formazane, azomethine, Nitroaryl, dioxazin, triphendioxazin, phenazin and stilbene dyes belong to. Such dyes have been extensively described in the literature, for example in EP-A-0 513 656, and familiar to the person skilled in the art.

Unless otherwise stated, these are in the examples below parts listed parts by weight.

example 1

In 2800 parts of a spin viscose with a cellulose content of 8.9%, one Alkali content of 5% and a viscosity of 38 falling seconds over 20 cm at 30 ° C 50 parts of a polyethyleneimine with a medium Molecular weight from 3000 to 5000, which was reacted with epichlorohydrin (24%), added. The polyethyleneimine was prepared according to Example 1 U.S. Patent No. 4,588,413.

After degassing, the spinning mass is made using the usual viscose spinning process into a bath containing sulfuric acid, sodium and zinc sulfate spun, stretched in acidic baths, cut, washed, prepared and dried.  

10 parts of these dry viscose fibers are then in a dyeing machine mixed with 100 parts of water. The mixture is heated to 60 ° C. and metered overall 0.1 parts of a 50% electrolyte-containing (mainly sodium-containing) Dye powder of the formula known from DE-A-19 43 904

over a period of 30 min. After a follow-up time of 5 min drained colorless remaining liquor and the material by usual methods washed out and dried. A deep red color is obtained with a strong color very good fastness properties.

Example 2

10 parts of the viscose fibers modified according to Example 1 are in transferred to a dyeing machine and in a liquor ratio of 1:10 with a treated aqueous liquor, which - based on the weight of the dry Ware - 0.1 parts of a reactive dye of the formula known from the DE-A-24 12 964

contains dissolved. The fiber mixture is dyed at 60 ° C. for 30 minutes. The The dyeing thus produced is further treated by rinsing and soaping in the usual way. A deep blue color with very good results is obtained Fastness to use.  

Example 3

It is a viscose spinning mass as described in Example 1 with a Reaction product from polyethyleneimine (molecular weight 3000 to 5000) and Epichlorohydrin manufactured.

After degassing, the spinning mass is made using the usual viscose spinning process into a bath containing sulfuric acid, sodium and zinc sulfate spun, stretched in acidic baths, cut, washed, prepared and dried.

After weaving, a textile viscose fabric is obtained, which is directly in one Dyeing process can be processed by the block method.

For this purpose, an aqueous dye solution containing 20 parts of the in 1000 parts by volume Dye of the formula

known from EP-A-0 158 233, Example 1, and 3 parts of a commercially available contains non-ionic wetting agent dissolved, by means of a foulard with a Fleet absorption of 80%, based on the weight of the fabric, at 25 ° C applied to the fabric. The fabric padded with the dye solution is wrapped on a dock, wrapped in plastic wrap and during 4 Let sit at 40 to 50 ° C for hours and then with cold and hot Water, which may contain a commercial surfactant, and optionally then rinsed again with cold water and dried.

A strong, uniformly colored yellow color is obtained, the good one General fastness properties, especially good rub and light fastness properties.  

Example 4

It is a viscose spinning mass as described in Example 1 with a Reaction product from polyethyleneimine (molecular weight 3000 to 5000) and Epichlorohydrin manufactured.

After degassing, spinning, stretching, cutting, washing and drying a fiber is obtained which is dyed by a customary drawing process can be. For this, 20 parts of the pretreated viscose fiber are combined in one Dyeing machine treated with 200 parts of an aqueous liquor, which - based on the weight of the dry goods - 1.5% of the reactive dye of the formula

known from EP-A-0 061 151, example 4, in commercial form and Contains texture. The fiber is dyed with this liquor at 60 ° C. for 30 minutes. The dyeing thus produced is further treated by rinsing and soapy in the usual way. The result is a lively orange color with the for Reactive dyes usually have good fastness properties.

Example 5

It is a viscose spinning mass as described in Example 1 with a Reaction product from polyethyleneimine (molecular weight 3000 to 5000) and Epichlorohydrin manufactured.

From an alkali cellulose prepared according to the information in Example 4 after the usual process steps for spin viscose a fiber material modified viscose manufactured without salt and alkali additives in one Exhaust process is colored reactive. For this you wrap 30 parts Viscose fiber on a bobbin and treats the yarn in one  Yarn dyeing machine, the 450 parts (based on the weight of the goods) one Fleet, the 0.6 parts, based on the initial weight of the goods, one electrolyte-containing dye (predominantly containing sodium chloride) of the general formula

known from DE-A-28 40 380, Example 1, contains and heats to 60 ° C, the fleet alternating from the inside out and the outside in is pumped. After 60 minutes at this temperature, the liquor is drained off and rinsed and washes the color obtained after the usual conditions. Man receives a yellow colored fiber with the general good fastness properties for Reactive dyes.

Further examples

The procedure for modifying the viscose is as described in the example 4 and dyes using the reactive dyes listed below by conventional methods, but without alkali or salt additives and receives similar good results, as in the previous examples.

Claims (10)

1. Modified regenerated cellulose fibers, produced by adding a modifier to a cellulose solution and from the solution, or by adding a modifier to a viscose solution and spinning fibers by the viscose spinning process, characterized in that the modifier is a polyethyleneimine of the formula (I) wherein
X is hydrogen or a radical of the formula - (CH₂-CH₂-NH) _c -H,
a is a number from 50 to 600 and
c is a number from 0 to 50,
or a reaction product of a polyethyleneimine of formula (I) with a bifunctional alkylating agent of formula (II) is A-ZA (II) wherein
A is a group of the formula -CH₂-Y, in which Y is a substituent which can be split off as an anion or a group which can be split off as an anion and Z is a direct bond or for a divalent straight-chain or branched radical of the formula (III) -C _n H _2n - ( III) where n is a number from 1 to 4,
a divalent radical of the formula (IV) -C _m H _2m -DC _m H _2m - (IV)
wherein m represents the numbers 1 or 2 and D represents -O-, -S-, -NH-, -CO-, -SO-, -SO₂- or phenylene;
or is a polymeric reaction product of an epihalohydrin with ammonia or with an amine of the formula (V) wherein
A is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms,
R alkyl with 1 to 5 carbon atoms, hydroxyalkyl with 1 to 5 carbon atoms, a group of the formula a group of the formula where n is a number from 0 to 5 and
X represents oxygen or sulfur;
or R and A together or an aliphatic heterocycle, which can also contain a further heteroatom from the group O, S and N,
and alkylene are each C₁-C₆ alkylene. 2. Modified regenerated cellulose fibers according to claim 1, characterized in that Y is chlorine, bromine, iodine, -OH, a sulfato group, a sulfonyloxy group, preferably a phenylsulfonyloxy group or p-tolylsulfonyloxy group, or the epoxy group is. 3. Modified regenerated cellulose fibers according to claim 1 or 2, characterized characterized in that a reaction product of a polyethyleneimine Formula (I) a bifunctional alkylating agent from the group Epichlorohydrin, glycid, 1,3-dichloropropan-2-ol, β, β′-dichloro-diethyl ether, β, β′-dichloro-diethylamine, β, β′-dichloro-diethylsulfide, β, β′-dichlorodiethylsulfoxide, β, β′-dichloro-diethylsulfone, β, β′-disulfatoethyl ether, β, β′-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzene, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxy-2-methylbutane and Diepoxypropylamin is used. 4. Modified regenerated cellulose fibers according to claim 3, characterized characterized in that the polyethyleneimine of formula (I) with the bifunctional Alkylating agent in a weight ratio of 100: 0.01 to 100: 2, preferably 100: 0.1 to 100: 1. 5. Modified regenerated cellulose fibers according to at least one of the Claims 1 to 4, characterized in that the modifier Has a molecular weight of at least 1000.   6. Modified regenerated cellulose fibers according to at least one of the Claims 1 to 5, characterized in that the amount of the in Cellulose fibers incorporated modifier 0.1 to 20 wt .-%, preferably 1 up to 10 wt .-%, based on the total weight of the modified Cellulose fibers. 7. Modified regenerated cellulose fibers according to at least one of the Claims 1 to 6, characterized in that said cellulose fibers according to be spun using a viscose spinning process. 8. Modified regenerated cellulose fibers according to at least one of the Claims 1 to 6, characterized in that said cellulose fibers according to the cupro process or the lyocell process. 9. Process for dyeing and printing fiber materials with water-soluble textile dyes, characterized in that the Coloring with a dye solution that is free of additional electrolyte salts and additional alkali, and using one of at least one of the Claims 1 to 8 modified cellulose fiber material. 10. The method according to claim 9, characterized in that the dye contains a fiber reactive group.